Ethers of fatty acid esters



Patented 1....14, 1941 for use as wetting, I

It relates more particularly to new agents.

PATENT. OFFICE s'rnsas or-ra'rrr non) ns'rans Melvin De Groote, University City, and Bernhard Keiser and Charles M.

assignors, to Petrolite Corporation, Ltd.,

Groves, M0,,

Delaware Blair, In, Webster by mesne assignments, a corporation or No Drawing. Application ril 19, loss,

. Serial No. 202,986

a I 12 Claims. (01. 260-404 This-invention relates to new products adapted dispersing or emulsifying ethereal condensation products of partially esterirled alkylolannnes having atleast one esteriiied hydroxyl group and at least one rreehydrox'yl group with partially alcohols, similarly having at least hydroxyl' group and 0 group; and it esterlfled polyhydric atleast oneiree hydroxyl includes not only these new products, but also a new process for their preparation.

The new products are quite ly eflective in acid solution.

Thenew products oi. the present invention alicyclic, or aralkylol or esterifled aralkylol; the

We represent 3 15 maybe represented by the formula:-

alicyclic, alkylol,

alkyl, alicyclic ,or aralkyl, alike or diilerent; Y. is anacyl group (higher or lower) 5 or, ii I! is an droxyalicyclic esteriii'ed alkylol, aralkylol or hygroup, Y may be hydrogen or acyl,

and Z is'the residue of a partially esteriiied polyhydric alcohol, such as a mono- I acid ester of ethylene or propylene glycol, or a residue of the nature of polyglycol, glycerol glycol,

amono-fatty and polyglyce one alcoholic or diglyceride, or.

polyglycerol, polyglycol glycerol, roi glycol residues,,having at least hydroxyl esterifled by a iatty acid,

advantageously a higher fatty acid corresponding to those occurring in natural rats .or oils.

These new duced by alkylolamine alcohol, in a0 40 l products are advantageously pro- "reaction between the corresponding and partially esterifled polyhydric cordance with the equation:

- g with elimination or water between an OH. group or the allrylolamine and an OR. group or the polyhydric alcohol, This reaction may with formation or an ether. be caused to take place by heatingtthe constituents together to a temperature in excess or C. but below the volatilization 0., advantageously, above point oi decomposition or 01 the constituents, tor a relativei to dry nitrogen,

may be passed throush the reac- In general, they may be represented I mula: one estei'ifled stable and are highin which a a: and a:

- least one OH (alcoholic compounds having .erin in natural scribing the present invention tion mixture to cause the reaction to proceed more rapidly.

' The partially esterifled alkylolamines used for the preparation or the. new products or the present invention may be preparedin various ways.- 5

\N R" A Rs ,7 1', I I I are al'lsyl groups as herein defined, or substituted 'allryl groups, which may be the same or diflerent, at least'one or which has at least one RiCOO substituent (Rs representing methyl or the carbon-linked chain of a one or which has at hydroxyl) substituent, an R4000 substituent, and an Old substituent in the same substituted alkyl group, with the other alkyl groups substituted or unsubstituted, being included. I I

In this specification and the appended claims, the term "fatty acid" is used to designate.broadly carboxylic acids of the aliphatic series, including 25 both unsaturated and saturated acids as well as the substituted acids which may occur in natural fats or oils, such as ricinoleic acid, and modifies tions oi the acids which occur. in natural oils, such as those in blown or bodied oils; and the term "higher fatty acid" is used to designate those carboxylc acids, generally having at least 8 carbon atoms, which occur combined with glyc-f oils and iats. It is understood that {the terms alkylol and alkyl" are used conventionally in chemistry to refer to 9 1mm. compounds which are non-cyclic and aliphatic in nature. We have round, however, that the alicyclic and hydroxyalicyclic, as well as the aralkyl and aralkylol' amines are, with respect to the reactions involved in the various phases oi the present invention, similar to the corresponding alkyl and alkylol amines, with the limitation that the aralkyl an'd aralkylol compoundshave the linkage to the nitrogen'atom in the side chain. For thisv reason, for the purpose oi de- I only, it is understood that the terms alkyl" and "alkylol" include within their scope alicyclic, aralwl, hydroxyalicyclic and aralkylol groups.

One advantageous method 0! preparing the partially 'esterifled alkylolamines is that described in our application Serial No. 180,993,1lled December 21, l937,by.re'action betweena triglyeeride of a fatty acid, or other ester 0! a 6 fatty acid) and at least that is, with three a through carbon ato eluded among the amine, diethanola ethylamine, dleth holic hydroxyl of the partially esterified' amine is available for condensation with a corresponding hydroxyl group of a partially esterified polyhydric alcohol in accordance with the present invention, the term partially esterified polyhydroxy alcohol" being similarly used to designate polyhydroxy alcohols having at least one esterifled hydroxyl group and at least one free hydroxyl group. However, the preparation of the partially esterified alkylolamines which may be used is not limited to the procedure described in said prior application, as they may also be prepared by suitable reaction between an acyl halide, such as acyl chlorides, and a tertiary alkylolamine, or in other ways. Also, it is to be understood that the alkylolamines used in accordance with the present invention need not be esters of tertiary' alkylolamines with the higher fatty acids, but include tertiary alkylolamines partially esterifled with the lower fatty acids, such as acetic acid, propionic acid, butyric acid, etc.

Similarly, the partially esterifiedv polyhydric alcohols used in accordance with the present invention may be prepared in any of the known ways, including the re-esterification of fats or oils by heating a polyhydric alcohol, such as glycerin or glycol with a fat or oil in the presence of a suitable catalyst, such as a basic salt; by the reaction of a fatty acid with a polyhydric alcohol in'the presence of a suitable condensing agent, the proportions of fatty acid and polyhydric alcohol being regulated so that after the resulting esteriflcation there remains a free alcoholic hydroxyl group in the major portion of the polyhydric alcohol residues, or in other ways. 7 A particularly advantageous method of preparing a mixture of partially esterified alkylolamine and partially esterifled polyhydric alcohol for reaction to form the new ethereal prodnets of the present invention is that described in our application Serial No. 191,964, filed February 23, 1938, in which a mixture of a fatty acid ester of a-polyhydric alcohol, a polyhydric alcohol, and a tertiary alkylolamine having more than one alcoholic hydroxyl group are heated together for a suflicient period of time to permit substantial alcoholysis to take place, with the production of a product consisting predominantly of partially esterifled tertiary alkylolamine and partially esterifled polyhydric alcohol, with a certain amount of unreacted alkylolamine, un-

reacted polyhydrlc alcohol ester and unreacted polyhydric alcohol. Such a mixture is admirably adapted for the production of the new products of the present invention, as the new products are readily prepared by simple extended heating of the'mixture.

.Among the amines which may be partially esterified for use in the production of the new products oi the present invention are a wide range of tertiary alkylol and tertiary alkyl alkylolamines. The two essentials are that the alkylolamine contain at least two alcoholic hydronl groups, which -may be attached to the same or different carbon chains, and be atertiary amine,

droxyl group. Typi be used are the following:

(C: H|OH):N

'Iriethanolamiue (0.11.011)

( C :HcO H) N (elm)- Dlethanolethylumine (021140 (ca om-N O Diethanolmethylamine tcimwamm 'lri-dih 'dro ropylamine yo i-gamma) KCaHK M lcimwmiaw (CI J) Di-dih droxy'pi'ogylethylamino (d lycerylet ylemine) Dihydrorypro yldiethylaniine (glyceryl othylamine) cm OHhN Triprop molamlne C Di-phenylpropnofihyiamine (CaHaOH) (CzHaQH)-N cH 00H cycloh xamiidle lamina OHIO HM (cam Dicyclohexanoicthylamlne oimo 11 SN Ti ibu (C4HIOH)\ reason):

0H Dibutanh thano lamifie CHI Dibutanolmethylamlno amin es', such as I tripropanolamine, ohexanoldiethanole, etc. All such by known procem are tertiary amines havcoholic hydroxyl groups, thus form esters with higher fatty acids, such esters having at least one free hycal of the amines which mar such as thylene glycol,

naturally occurring triglycerides,

: in producing cation oi such i i v arcane? Any of the available partially esterifled polyhydric alcohols may be used in the production or the new compositions in accordance with the present invention. Products produced by the use'ot monoor dlglycer'idesr superglycerinslted fats, or the like have important advantages. Monoor'di'glycerides may be readily produced by the re-esterification or suprglycerination of oil, perili-a oil, etc., as

tics due to the presence of oxygen in the long hydrocarbon chain characteristlcoi the fatty acids.

Partially esterifledpolyhydric alcohols useful the new products 0! the present invention may also be produced by the re-esteriflwith polyhydric alcohols other than glycerin, Pr py e e glycol. polyglycerols, polyglycols, glyce'ryl glycol ethers. lycol ethers, glycerol polyglycol ethers, etc; In general. such production of the partially esterifled polyhydric alcohols desired polyhydric alcohol in the presence of a suitable catalyst, in accord- 1 alkylolarnine having more tial starting material.

I to

useful ance with well known practice. partially esterlfled polyhydric alcohols which may be usedare not limited to those in which the fatty acid group is that oi a higher, naturally occurring iatty'acid such and oils, but includes polyhydric alcohols partially esterlfied by the lower fatty acifi, such as acetic acid, propionic acid, etc. Thus for example, partialiy esteriiied polyhydrlc alcohols in carrying out the present invention may be prepared from .triacetin, or ironic. p yhydric alcohol and acyl chlorides, such as acetyl chloride, or in other suitable ways, as from a chlorhydrin' and a suitable fatty acid.

- if the partially esterified polyhydrlc alcohol, or the partially esterifled alkylolamine, has more than one free alcoholic hydroxyl group, more complex condensation products may be produced in the course of the reaction, as by the condensation of one molecule of a-partially esterined than one tree hy wxyl group with one molecule of partially ed polyhydric alcohol and one molecule'ol the amine. or with two molecules polyhydric alcohol; or one molecule of the partially esterified polyhydric alcohol, having more thanone tree hydroxyl group, glyceride, may condense with the mine. In any cue, tion productsare ethereal such as'a monotwo molecules oi derivatives or the ini- '-'Ihe' invention will be further illustrated by the folio ing specific examples, although it is not limited thereto. r

Example 1.--0ommercial triethanolamine, cocoanut oil 'and glycerin in the propor ions 0! one mdleoi cocoanutoil to three moles of amine and at least one mole of glycerin are including such as corn'oil, rapev seed oil, soya bean oil, sunflower in which R represents the long toalkalies.

two hours at atemperature olaround 150 to C. To the product so predominantly of the the trlgiyeeryia triglycerides as those listed above triglycerylamine and the is accomplished by heating the triglycerides with the However, the

.sents the carbon as occurs innatural fats bBt nt ial amounts of of the par ally ed the remand coedand 180 C. lor about triethanolhated to a temperature at between about 150 and 180 C. for a period of about titty hours; It desired, a current of dry nitrogen may be passed through the reaotion mixture. The resulting product contains a al and pr p nderatin: amount oi the ether resulting from the con-= densation oi the mono iatty ,acid ester oft-riethanolamine and the monov and di-iatty acid ester of glycerin, shown in the following formula: I J

acoocim 'N-c.m-o on;-c,m(on)(o oc R) social chain of the cocoanut oil iatty acids.

The product has extremely good wetting, emulsilying and detergent properties, is highly eflective in acid solution and shows good resistance Example 2.'l;iglycerylamine (tri-dihydroxypropylamine) and castor oil are reacted in the proportions of three moles of castor oil to two moles of triglycerylanilnaior a period of about produced, which consists di-ricinoleic acid ester cl is added about 50% of the mono-ricinoleic'acidester oi glycerin, and the resulting mixture is heated to about 150 to C. for about two days, with the production of carbon linked" mixed ethers. of the'di-ricinoleic acid ester of mono-ricinoleic acid ester of glycerimoi the type formula:

in'which two of the M's represent the acyl group corresponding to ri 7 three represent hydrosemand in which R. reprelinked chain characteristic of ricinoleic acid.- 7

Example 3.Palm kerrieloil and diethanolethylamine, in the molecular prop rtions of three moles of the amine to one mole of the palm kernel oil are heated together with one mole of a polyglycerol to a temperature bet about 150 and 180 C. for about two days with the production or a reaction product containing a large proportion of the ether of the mono iattil acid ester of diethanolethylamine and themono-' glyceride corresponding to palm kernel oil, and a large proportion oi the ether of the same diethanolethylamine ester and the monoacid ester of the pfilyfllycerol.

Ecample d.-An equimolecular mixture of the monoacetic acid ester of tri'ethanolamine and the monostearic acid ester of glycerin are. heated together for a period 0! about hity hours, with the production of a product containing the ether of the forfatty mule:

cnicoocim v v a n-csmoo nuomooo c 111 noc=m together with more complex ethereal derivatives or the amineand tho monoglyceride.

Example 5. trieth laminepa fatty oil and lone glycol proportions of t molw olthe e to one mole oi the oil to one mole of the ethylene glycol V are heated to a temperature about 150 duction or a reaction product containing substantial amounts of theether oi the mono-ester ,ss (R000) (OHlCaI-BO camowmcamomin oleic acid and the other as J inthemolecular' two ,dayswith the pro=' 4 of triethanolamine with the corresponding mono-glyceride and the ether of the mono-ester of triethanolamine with the mono-ester of ethylene glycol. I

The. foregoing examples illustrate the production of certain 01 the new products .of the present invention. In place of the partially esterifled tertiary alkylolamine of the examples, any other available tertiary alkylolamines having at least one esterifled hydroxyl group and at least one free hydroxyl group, such as the products obtained by the partial esterification of the polyhydroxy alkylolamines previously referred to may be used; while in place of the partially esterified polyhydric alcohols of theexamples, otherpartially esterified polyhydric alcohols may be used; including those previously referred to.

general, ethers derived from monoor diglycerides and partially esterii ied tertiary alkylolamines, particularly triethanolamine, have important advantages.

We claim:

' 1. Ethers of partially esterified tertiary'alkylolamines with partially esterified polyhydric alcohols.

2. Ethers of partially esterified tertiary alkylolamines with compounds of the class consisting of mono- 3. Ethers of partially esterifled triethanolamines with partially esterified polyhydric aicohols. I

4. Ethers of partially esterifled triet'hanolamines with compounds of the class consisting of monoand diglycerides.

5. Ethers of mono-fatty acid esters of tertiary alkylolamines having more than one hydroxy group with partially esterified polyhydric alcohols.

azaaea'r and diglycerides of iatty acids.

6. Ethers of mono-fatty acid esters of triethanolamine with compounds of the class consisting of monoand diglycerides.

7. Ethers of mono-fatty acid esters of triethanolamine with compounds of the class con- 5 sisting of monoand diglycerides of higher fatty acids. Y

' 8. Ethereal reaction products .of partially esterified. tertiary alkylolamines and partially esteriiied polyhydric alcohols. v

9. Ethereal reaction products of compounds or the class consisting of monoand diglycerides with mono-fatty acid esters of triethanolamine.

' 10. Ethereal reaction products of compounds of the class consisting of monoand diglycerides with di-fatty acid esters of triethanolamine.

11. The process of preparing wetting, emulsilying and dispersing agents which comprises heating a triglyceride, a tertiary alkylolamine having more than one alcoholic hydroxyl and a polyhydric alcohol to a temperature in excess of 100 C. for a period of time suflicient to cause alcoholysis of the triglyceride and condensation between the resulting partially esterifled alkylolamine and partially ester-ified glycerin.

12. The process 01 preparing wetting, emulsifying and dispersing agents which comprises heating a partially esterifled tertiary alkylplamine with a partially esterified polyhydric aicohol for a period of time suflicient to eilectso condensation of the said alcohol with the said amine, with the productiom of an ethereal reaction product. 1

'MELvm DE GROOTE.

B KEISER. CHARLES M. BLAIR, JR. 

